CA2661407C - Procede de fabrication de derives d'acide 3-dihalogenomethyl-pyrazol-4-carboxylique - Google Patents
Procede de fabrication de derives d'acide 3-dihalogenomethyl-pyrazol-4-carboxylique Download PDFInfo
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- CA2661407C CA2661407C CA2661407A CA2661407A CA2661407C CA 2661407 C CA2661407 C CA 2661407C CA 2661407 A CA2661407 A CA 2661407A CA 2661407 A CA2661407 A CA 2661407A CA 2661407 C CA2661407 C CA 2661407C
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- CA
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- Prior art keywords
- enyl
- alkyl
- general formula
- formula
- aryl
- Prior art date
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000002841 Lewis acid Substances 0.000 claims abstract description 15
- QXHXMALPRIXDEU-UHFFFAOYSA-P [3-(dimethylamino)-2-[(dimethylazaniumyl)methyl]prop-2-enyl]-dimethylazanium Chemical class CN(C)C=C(C[NH+](C)C)C[NH+](C)C QXHXMALPRIXDEU-UHFFFAOYSA-P 0.000 claims abstract description 15
- 150000007517 lewis acids Chemical class 0.000 claims abstract description 15
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims description 15
- 229910052717 sulfur Inorganic materials 0.000 claims description 14
- 229910052731 fluorine Inorganic materials 0.000 claims description 12
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 229910052801 chlorine Inorganic materials 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 6
- 239000000543 intermediate Substances 0.000 claims description 5
- 238000002955 isolation Methods 0.000 claims description 4
- 150000001450 anions Chemical class 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 2
- 150000002429 hydrazines Chemical class 0.000 abstract description 7
- -1 carbonyl halides Chemical class 0.000 description 74
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 33
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 29
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 14
- 125000005842 heteroatom Chemical group 0.000 description 14
- 229910052698 phosphorus Inorganic materials 0.000 description 13
- 150000003839 salts Chemical class 0.000 description 13
- 239000002904 solvent Substances 0.000 description 13
- 150000002148 esters Chemical class 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 239000000460 chlorine Substances 0.000 description 8
- 239000011737 fluorine Substances 0.000 description 8
- 101150041968 CDC13 gene Proteins 0.000 description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 7
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 7
- 125000003545 alkoxy group Chemical group 0.000 description 7
- 125000003368 amide group Chemical group 0.000 description 7
- 125000003118 aryl group Chemical group 0.000 description 7
- 229910052736 halogen Inorganic materials 0.000 description 7
- 150000002367 halogens Chemical class 0.000 description 7
- HDZGCSFEDULWCS-UHFFFAOYSA-N monomethylhydrazine Chemical compound CNN HDZGCSFEDULWCS-UHFFFAOYSA-N 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- VIRGYRZBWQFJGJ-UHFFFAOYSA-N 1,1,2,2-tetrafluoro-n,n-dimethylethanamine Chemical compound CN(C)C(F)(F)C(F)F VIRGYRZBWQFJGJ-UHFFFAOYSA-N 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 125000004093 cyano group Chemical group *C#N 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 6
- 150000003568 thioethers Chemical class 0.000 description 6
- 125000002252 acyl group Chemical group 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 5
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 4
- 125000002877 alkyl aryl group Chemical group 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 4
- 125000000304 alkynyl group Chemical group 0.000 description 4
- 125000003710 aryl alkyl group Chemical group 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 238000004293 19F NMR spectroscopy Methods 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- JODDVGWNUWGSMG-UHFFFAOYSA-N ethyl 2-(dimethylamino)prop-2-enoate Chemical compound CCOC(=O)C(=C)N(C)C JODDVGWNUWGSMG-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 2
- ULGZDMOVFRHVEP-RWJQBGPGSA-N Erythromycin Chemical compound O([C@@H]1[C@@H](C)C(=O)O[C@@H]([C@@]([C@H](O)[C@@H](C)C(=O)[C@H](C)C[C@@](C)(O)[C@H](O[C@H]2[C@@H]([C@H](C[C@@H](C)O2)N(C)C)O)[C@H]1C)(C)O)CC)[C@H]1C[C@@](C)(OC)[C@@H](O)[C@H](C)O1 ULGZDMOVFRHVEP-RWJQBGPGSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 2
- 125000002820 allylidene group Chemical group [H]C(=[*])C([H])=C([H])[H] 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- ANTPVARYELNKNQ-UHFFFAOYSA-N ethyl 3-(diethylamino)prop-2-enoate Chemical compound CCOC(=O)C=CN(CC)CC ANTPVARYELNKNQ-UHFFFAOYSA-N 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- SWADNLFRTHBCLE-UHFFFAOYSA-N n,n-diethyl-1,1,2,2-tetrafluoroethanamine Chemical compound CCN(CC)C(F)(F)C(F)F SWADNLFRTHBCLE-UHFFFAOYSA-N 0.000 description 2
- BNTFCVMJHBNJAR-UHFFFAOYSA-N n,n-diethyl-1,1,2,3,3,3-hexafluoropropan-1-amine Chemical compound CCN(CC)C(F)(F)C(F)C(F)(F)F BNTFCVMJHBNJAR-UHFFFAOYSA-N 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 125000006710 (C2-C12) alkenyl group Chemical group 0.000 description 1
- 125000006711 (C2-C12) alkynyl group Chemical group 0.000 description 1
- COLOHWPRNRVWPI-UHFFFAOYSA-N 1,1,1-trifluoroethane Chemical compound [CH2]C(F)(F)F COLOHWPRNRVWPI-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 1
- OOJZGFFJNPGACA-UHFFFAOYSA-N 2-chloro-1,1,2-trifluoro-n,n-dimethylethanamine Chemical compound CN(C)C(F)(F)C(F)Cl OOJZGFFJNPGACA-UHFFFAOYSA-N 0.000 description 1
- XSJVWZAETSBXKU-UHFFFAOYSA-N 2-ethoxypropane Chemical compound CCOC(C)C XSJVWZAETSBXKU-UHFFFAOYSA-N 0.000 description 1
- ZKKBIZXAEDFPNL-UHFFFAOYSA-N 3-(dimethylamino)prop-2-enenitrile Chemical compound CN(C)C=CC#N ZKKBIZXAEDFPNL-UHFFFAOYSA-N 0.000 description 1
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229910021630 Antimony pentafluoride Inorganic materials 0.000 description 1
- 125000006539 C12 alkyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 101150032866 CDC11 gene Proteins 0.000 description 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- IGQNDARULCASRN-UHFFFAOYSA-N Fluxapyroxad (bas 700 f)-tp cscd465008 Chemical class OC(=O)C1=CNN=C1C(F)F IGQNDARULCASRN-UHFFFAOYSA-N 0.000 description 1
- LELOWRISYMNNSU-UHFFFAOYSA-N Hydrocyanic acid Natural products N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 1
- 229910021174 PF5 Inorganic materials 0.000 description 1
- 229910008046 SnC14 Inorganic materials 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-N acetoacetic acid Chemical compound CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000012868 active agrochemical ingredient Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- VBVBHWZYQGJZLR-UHFFFAOYSA-I antimony pentafluoride Chemical compound F[Sb](F)(F)(F)F VBVBHWZYQGJZLR-UHFFFAOYSA-I 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001733 carboxylic acid esters Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229960001701 chloroform Drugs 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000002188 cycloheptatrienyl group Chemical group C1(=CC=CC=CC1)* 0.000 description 1
- 150000001934 cyclohexanes Chemical class 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- MVUMJYQUKKUOHO-AATRIKPKSA-N ethyl (e)-3-(dimethylamino)prop-2-enoate Chemical compound CCOC(=O)\C=C\N(C)C MVUMJYQUKKUOHO-AATRIKPKSA-N 0.000 description 1
- CBDPWKVOPADMJC-UHFFFAOYSA-N ethyl 4,4-difluoro-3-oxobutanoate Chemical compound CCOC(=O)CC(=O)C(F)F CBDPWKVOPADMJC-UHFFFAOYSA-N 0.000 description 1
- 235000019439 ethyl acetate Nutrition 0.000 description 1
- WHRIKZCFRVTHJH-UHFFFAOYSA-N ethylhydrazine Chemical compound CCNN WHRIKZCFRVTHJH-UHFFFAOYSA-N 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- MVPDNJQLPITPIX-SNAWJCMRSA-N methyl (e)-3-(dimethylamino)prop-2-enoate Chemical compound COC(=O)\C=C\N(C)C MVPDNJQLPITPIX-SNAWJCMRSA-N 0.000 description 1
- BTTXESIFAHCXMK-UHFFFAOYSA-N methyl 2-methoxyprop-2-enoate Chemical compound COC(=C)C(=O)OC BTTXESIFAHCXMK-UHFFFAOYSA-N 0.000 description 1
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 150000004812 organic fluorine compounds Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 230000035899 viability Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Plural Heterocyclic Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
L'invention concerne un procédé de fabrication de dérivés d'acide 3-dihalogénométhyl-pyrazol-4-carboxylique de formule (I) par réaction de .alpha.-fluoroamines de formule (III) en présence d'acides de Lewis avec des dérivés d'acide acrylique de formule (II) pour former des sels de vinamidinium de formule (IV) et par leur réaction ultérieure avec des hydrazines, ainsi que les sels de vinamidinium de formule (IV) eux-mêmes.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102006039909A DE102006039909A1 (de) | 2006-08-25 | 2006-08-25 | Verfahren zum Herstellen von 3-Dihalomethyl-pyrazol-4-carbonsäurederivaten |
| DE102006039909.9 | 2006-08-25 | ||
| PCT/EP2007/007377 WO2008022777A2 (fr) | 2006-08-25 | 2007-08-22 | Procédé de fabrication de dérivés d'acide 3-dihalogénométhyl-pyrazol-4-carboxylique |
Publications (2)
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| CA2661407A1 CA2661407A1 (fr) | 2008-02-28 |
| CA2661407C true CA2661407C (fr) | 2014-07-15 |
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| CA2661407A Active CA2661407C (fr) | 2006-08-25 | 2007-08-22 | Procede de fabrication de derives d'acide 3-dihalogenomethyl-pyrazol-4-carboxylique |
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| EP (1) | EP2057126B1 (fr) |
| JP (2) | JP5511380B2 (fr) |
| KR (1) | KR101445326B1 (fr) |
| CN (1) | CN101506173B (fr) |
| AT (1) | ATE487702T1 (fr) |
| BR (1) | BRPI0715674B1 (fr) |
| CA (1) | CA2661407C (fr) |
| DE (2) | DE102006039909A1 (fr) |
| DK (1) | DK2057126T3 (fr) |
| ES (1) | ES2355309T3 (fr) |
| IL (1) | IL196894A (fr) |
| MX (1) | MX2009001840A (fr) |
| RU (1) | RU2470015C2 (fr) |
| TW (1) | TWI419880B (fr) |
| WO (1) | WO2008022777A2 (fr) |
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| BRPI0812054B1 (pt) | 2007-06-01 | 2015-12-29 | Basf Se | processo de preparação de (3-di-halometilpirazol-4-il) carboxamidas n-substituídas |
| JP5559678B2 (ja) * | 2007-06-15 | 2014-07-23 | ビーエーエスエフ ソシエタス・ヨーロピア | ジフルオロメチル置換ピラゾール化合物の製造方法 |
| US8481778B2 (en) | 2007-08-16 | 2013-07-09 | Solvay (Societe Anonyme) | Process for the preparation of esters of 4-fluorosubstituted 3-oxo-alcanoic acids |
| EP2133341A1 (fr) * | 2008-02-25 | 2009-12-16 | Bayer CropScience AG | Procédé de synthèse régiosélective de dérivés d'acides carboniques 1-alcyl-3-haloalcyl-pyrazol-4 |
| EP2100883A1 (fr) | 2008-03-10 | 2009-09-16 | Bayer CropScience AG | Procédé de synthèse régiosélective de dérivés d'acides carboniques 1-alcyl-3-haloalcyl-pyrazol-4 |
| ES2386940T3 (es) * | 2008-05-02 | 2012-09-06 | Basf Se | Método para la preparación de ésteres halosustituidos de ácido 2-(aminometiliden)-3-oxobutírico |
| WO2009133178A1 (fr) | 2008-05-02 | 2009-11-05 | Basf Se | Procédé de fabrication d’esters de l’acide 2-(aminométhylidène)-4,4-difluoro-3-oxobutyrique |
| BRPI0911767A2 (pt) * | 2008-05-05 | 2015-07-28 | Basf Se | Processo, e, composto. |
| US8344157B2 (en) | 2008-07-21 | 2013-01-01 | Basf Se | Process for preparing 1,3-disubstituted pyrazolecarboxylic esters |
| GB0908435D0 (en) * | 2009-05-15 | 2009-06-24 | Syngenta Ltd | Processes |
| WO2011054732A1 (fr) | 2009-11-05 | 2011-05-12 | Basf Se | Procédé d'élaboration de composés de pyrazole 1,3-disubstitués |
| CN102596911B (zh) | 2009-11-05 | 2015-04-08 | 巴斯夫欧洲公司 | 制备缩醛胺的方法及其在制备1,3-二取代的吡唑化合物中的用途 |
| DK2560961T3 (en) | 2010-04-23 | 2017-02-20 | Bayer Ip Gmbh | METHOD FOR PREPARING 5-FLUORO-1-ALKYL-3-FLUORALKYL-1H-PYRAZOL-4-CARBOXYLYRIC CHLORIDE AND FLUORIDES |
| US20140128617A1 (en) | 2011-06-21 | 2014-05-08 | Wahed Ahmed Moradi | Method for producing pyrazolylcarboxanilides |
| EP2623496A1 (fr) | 2012-02-01 | 2013-08-07 | Bayer CropScience AG | Procédé de fabrication de dérivés d'acide 3,5-bis(fluoralkyl)-pyrazol-4 carbonique et 3,5-bis(fluoralkyl)-pyrazoles |
| MX355542B (es) | 2012-08-30 | 2018-04-20 | Bayer Cropscience Ag | Procedimiento de descarboxilacion de derivados de acido 3,5-bis(haloalquil)-pirazol-4-carboxilico. |
| US8871947B2 (en) | 2013-02-04 | 2014-10-28 | KingChem LLC | Preparation of alkyl 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid ester |
| JP6377727B2 (ja) * | 2013-05-22 | 2018-08-22 | バイエル・クロップサイエンス・アクチェンゲゼルシャフト | α，α−ジハロアミンからの３，５−ビス（フルオロアルキル）ピラゾール誘導体の製造方法 |
| JP6518654B2 (ja) * | 2013-05-22 | 2019-05-22 | バイエル・クロップサイエンス・アクチェンゲゼルシャフト | ３，５−ビス（フルオロアルキル）ピラゾール誘導体の製造方法 |
| TWI647215B (zh) * | 2013-11-11 | 2019-01-11 | 德商拜耳作物科學股份有限公司 | 自α,α－二鹵胺製備３,５－雙鹵烷基吡唑衍生物之方法 |
| WO2015085464A1 (fr) | 2013-12-09 | 2015-06-18 | King Chem, Llc | Procédé de préparation de 3-difluorométhyl-1-méthyl-1h-pyrazole-4-carboxylate d'alkyle et de ses analogues |
| EP3015458A1 (fr) | 2014-11-03 | 2016-05-04 | Bayer CropScience AG | Procédé de préparation de dérivés de 3,5-bis bis(haloalkyl)pyrazole à partir de a,a-dihaloamines et ketimines |
| EP3122727B1 (fr) * | 2014-03-24 | 2018-01-31 | Bayer CropScience Aktiengesellschaft | Procédé de préparation de dérivés de 3,5-bis(haloalkyl)pyrazole à partir d' alpha , alpha-dihaloamines et de cétimines |
| MX2016016399A (es) | 2014-06-11 | 2017-04-06 | Bayer Cropscience Ag | Proceso para la preparacion de 3,5-bis(haloalquil)pirazoles por medio de la acilacion de cetiminas. |
| MX2016016396A (es) | 2014-06-11 | 2017-04-06 | Bayer Cropscience Ag | Proceso para preparar derivados de 3,5-bis(haloalquil)pirazol por medio de la acilacion de hidrazonas. |
| CN104529899A (zh) * | 2014-12-19 | 2015-04-22 | 浙江泰达作物科技有限公司 | 高区域选择性制备1-烷基-3-卤代烷基吡唑衍生物的方法 |
| CN105541716B (zh) * | 2015-03-26 | 2024-02-23 | Ａｇｃ株式会社 | 吡唑衍生物的制造方法 |
| WO2016202254A1 (fr) * | 2015-06-19 | 2016-12-22 | 浙江永太科技股份有限公司 | Procédé de préparation d'un dérivé d'acide pyrazolecarboxylique, et intermédiaire correspondant |
| MX2017017140A (es) | 2015-06-26 | 2018-03-09 | Bayer Cropscience Ag | Proceso para la preparacion de pirazoles sustituidos que contienen grupos haloalcoxi-y haloalquiltio a partir de a,a-dihaloalquilaminas y quetiminas. |
| EP3178813A1 (fr) | 2015-12-09 | 2017-06-14 | Basf Se | Procédé de préparation de 3-oxocarboxylates halogéné portant un groupe 2-dialkylaminométhylidène ou 2-alkoxyméthylidène |
| WO2017125318A1 (fr) | 2016-01-21 | 2017-07-27 | Bayer Cropscience Aktiengesellschaft | Procédé de préparation de quinoléines polyfluoroalkylées |
| CN109689629B (zh) | 2016-09-21 | 2022-11-29 | 拜耳作物科学股份公司 | 制备3-氟烷基-5-吡唑羧酸酯和3-氟烷基-5-吡唑羧酸的方法 |
| WO2018234184A1 (fr) | 2017-06-22 | 2018-12-27 | Bayer Aktiengesellschaft | Procédé de préparation de quinoléines 2,3,4-trisubstituées |
| CN111566093A (zh) | 2017-12-22 | 2020-08-21 | 索尔维公司 | 吡唑甲酸衍生物及其前体的制造方法 |
| PT3797099T (pt) | 2018-05-21 | 2024-02-05 | Pi Industries Ltd | Método para preparar compostos heterocíclicos substituídos |
| CN112351972A (zh) | 2018-06-18 | 2021-02-09 | 拜耳公司 | 二取代的5(3)-吡唑羧酸酯及由烯醇酯和氟烷基氨基(far)试剂制备其的方法 |
| JP6911143B2 (ja) | 2018-11-07 | 2021-07-28 | 福建永晶科技股▲ふん▼有限公司Ｆｕｊｉａｎ Ｙｏｎｇｊｉｎｇ Ｔｅｃｈｎｏｌｏｇｙ Ｃｏ．， Ｌｔｄ | ピラゾール又はピリミジノンの新しい製造方法 |
| CN110577503A (zh) * | 2019-08-02 | 2019-12-17 | 宿迁市科莱博生物化学有限公司 | 一种卤素取代化合物及其制备方法和应用 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5489624A (en) | 1992-12-01 | 1996-02-06 | Minnesota Mining And Manufacturing Company | Hydrophilic pressure sensitive adhesives |
| DE4302156A1 (de) | 1993-01-27 | 1994-07-28 | Bayer Ag | Verfahren zur Herstellung von Aminomethylenverbindungen |
| US5359089A (en) * | 1993-12-22 | 1994-10-25 | American Cyanamid Company | Process for the preparation of 2,4,5-tribromopyrrole-3-carbonitrile |
| GB0101996D0 (en) * | 2001-01-25 | 2001-03-14 | Syngenta Participations Ag | Organtic compounds |
| DE10161978A1 (de) | 2001-12-17 | 2003-06-26 | Bayer Ag | Verfahren zur Herstellung von 2-Halogenacyl-3-amino-acrylsäure-derivate |
| KR100818540B1 (ko) * | 2002-03-05 | 2008-04-01 | 신젠타 파티서페이션즈 아게 | Ｏ-사이클로프로필-카복스아닐리드 및 이를 포함하는 살진균 조성물 |
| DE10349500A1 (de) | 2003-10-23 | 2005-06-02 | Bayer Cropscience Ag | Verfahren zum Herstellen von 2-Dihalogenacyl-3-amino-acrylsäureestern und 3-Dihalogenmethyl-pyrazol-4-carbonsäureestern |
| GB0415764D0 (en) | 2004-07-14 | 2004-08-18 | Syngenta Participations Ag | Chemical process |
| MX2007004638A (es) * | 2004-10-21 | 2007-06-08 | Syngenta Participations Ag | Proceso para la preparacion de pirazoles. |
| JP5559678B2 (ja) * | 2007-06-15 | 2014-07-23 | ビーエーエスエフ ソシエタス・ヨーロピア | ジフルオロメチル置換ピラゾール化合物の製造方法 |
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2006
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2007
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- 2007-08-22 US US12/438,732 patent/US7939673B2/en active Active
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- 2007-08-22 MX MX2009001840A patent/MX2009001840A/es active IP Right Grant
- 2007-08-22 DE DE502007005625T patent/DE502007005625D1/de active Active
- 2007-08-22 CA CA2661407A patent/CA2661407C/fr active Active
- 2007-08-22 DK DK07801808.2T patent/DK2057126T3/da active
- 2007-08-22 EP EP07801808A patent/EP2057126B1/fr active Active
- 2007-08-22 JP JP2009524958A patent/JP5511380B2/ja active Active
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Also Published As
| Publication number | Publication date |
|---|---|
| JP5805717B2 (ja) | 2015-11-04 |
| EP2057126A2 (fr) | 2009-05-13 |
| IL196894A (en) | 2015-03-31 |
| JP5511380B2 (ja) | 2014-06-04 |
| CN101506173B (zh) | 2012-05-30 |
| TWI419880B (zh) | 2013-12-21 |
| DE102006039909A1 (de) | 2008-03-13 |
| DK2057126T3 (da) | 2011-02-28 |
| JP2014001226A (ja) | 2014-01-09 |
| WO2008022777A8 (fr) | 2009-04-09 |
| JP2010501502A (ja) | 2010-01-21 |
| IL196894A0 (en) | 2009-11-18 |
| MX2009001840A (es) | 2009-03-03 |
| BRPI0715674A2 (pt) | 2013-07-09 |
| RU2470015C2 (ru) | 2012-12-20 |
| ES2355309T3 (es) | 2011-03-24 |
| EP2057126B1 (fr) | 2010-11-10 |
| CN101506173A (zh) | 2009-08-12 |
| US20090326242A1 (en) | 2009-12-31 |
| CA2661407A1 (fr) | 2008-02-28 |
| DE502007005625D1 (de) | 2010-12-23 |
| KR101445326B1 (ko) | 2014-09-29 |
| WO2008022777A2 (fr) | 2008-02-28 |
| WO2008022777A3 (fr) | 2008-04-17 |
| TW200817335A (en) | 2008-04-16 |
| US7939673B2 (en) | 2011-05-10 |
| RU2009110413A (ru) | 2010-09-27 |
| BRPI0715674B1 (pt) | 2015-06-16 |
| ATE487702T1 (de) | 2010-11-15 |
| KR20090043580A (ko) | 2009-05-06 |
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